CN114804030B - Preparation method and device of anhydrous hydrogen fluoride - Google Patents
Preparation method and device of anhydrous hydrogen fluoride Download PDFInfo
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- CN114804030B CN114804030B CN202210471104.5A CN202210471104A CN114804030B CN 114804030 B CN114804030 B CN 114804030B CN 202210471104 A CN202210471104 A CN 202210471104A CN 114804030 B CN114804030 B CN 114804030B
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910000040 hydrogen fluoride Inorganic materials 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 86
- 239000007788 liquid Substances 0.000 claims abstract description 65
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims abstract description 61
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 59
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 43
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 claims abstract description 40
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 37
- 239000002674 ointment Substances 0.000 claims abstract description 35
- 238000002425 crystallisation Methods 0.000 claims abstract description 27
- 230000008025 crystallization Effects 0.000 claims abstract description 27
- 239000012535 impurity Substances 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 21
- 239000006227 byproduct Substances 0.000 claims abstract description 20
- 230000035484 reaction time Effects 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- 239000002686 phosphate fertilizer Substances 0.000 claims abstract description 12
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 61
- 238000006243 chemical reaction Methods 0.000 claims description 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 42
- 238000001704 evaporation Methods 0.000 claims description 38
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 36
- 239000012452 mother liquor Substances 0.000 claims description 36
- 230000008020 evaporation Effects 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 23
- 238000005915 ammonolysis reaction Methods 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 21
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 20
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 238000000746 purification Methods 0.000 claims description 15
- 150000002506 iron compounds Chemical class 0.000 claims description 14
- 150000002611 lead compounds Chemical class 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 235000003270 potassium fluoride Nutrition 0.000 claims description 10
- 239000011698 potassium fluoride Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 229910000464 lead oxide Inorganic materials 0.000 claims description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 claims 1
- 230000023556 desulfurization Effects 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011737 fluorine Substances 0.000 abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- 238000009825 accumulation Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract 1
- 238000003541 multi-stage reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 88
- 238000001914 filtration Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 229940104869 fluorosilicate Drugs 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 239000010436 fluorite Substances 0.000 description 4
- 239000010413 mother solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 208000012839 conversion disease Diseases 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- -1 ammonium fluorosilicate Chemical compound 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D35/00—Filtering devices having features not specifically covered by groups B01D24/00 - B01D33/00, or for applications not specifically covered by groups B01D24/00 - B01D33/00; Auxiliary devices for filtration; Filter housing constructions
- B01D35/28—Strainers not provided for elsewhere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D36/00—Filter circuits or combinations of filters with other separating devices
- B01D36/003—Filters in combination with devices for the removal of liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/02—Crystallisation from solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/194—Preparation from ammonium fluoride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
- C01B7/196—Separation; Purification by distillation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention belongs to the technical field of fluorine chemical industry, and particularly relates to a preparation method and a device of anhydrous hydrogen fluoride. The invention adopts fluosilicic acid which is a byproduct in the phosphate fertilizer industry as a fluorine source to produce anhydrous hydrogen fluoride, the fluosilicic acid reacts with ammonia water to obtain ammonium fluosilicate solution after impurity removal, the ammonium fluosilicate solution reacts with the ammonia water and is evaporated, concentrated and thermally decomposed to obtain ammonium bifluoride molten liquid, the ammonium bifluoride molten liquid reacts with sodium fluoride to obtain sodium bifluoride ointment after cooling and crystallization, the sodium bifluoride ointment is dried and thermally decomposed to obtain crude hydrogen fluoride gas, and the crude hydrogen fluoride is purified to obtain the anhydrous hydrogen fluoride. Continuous production is realized through a multi-stage reaction flow, so that the yield of anhydrous hydrogen fluoride is effectively improved, and the reaction time is shortened. Through impurity removal treatment, the accumulation of impurities in the system is reduced, and side reactions in the system are avoided. In addition, the byproducts in the system are recycled, so that the production cost is reduced, the waste discharge is reduced, and clean production is realized.
Description
Technical Field
The invention belongs to the technical field of fluorine chemical industry, and particularly relates to a preparation method and a device of anhydrous hydrogen fluoride.
Background
At present, a fluorine source for producing hydrogen fluoride at home and abroad is still a strategic resource fluorite, and the strength of restricting exploitation of fluorite resources is increased in all countries. Therefore, how to develop new fluorine sources becomes a primary problem for the fluorine industry.
Fluorine is used as one of the elements associated with phosphate ore as the raw material of phosphorus chemical industry, and the content of fluorine is about 3-4% and is 10-20 times of fluorite reserves. A large amount of silicon tetrafluoride gas is produced in the production process of the phosphate fertilizer and is converted into fluosilicic acid after being absorbed by water. Therefore, the byproduct fluosilicic acid in the phosphate fertilizer industry is rich in resources and low in cost. The resource recycling of byproduct fluosilicic acid in industry in China starts in the 70 s, and a plurality of recycling process routes are developed after years of exploration and research, but the method mainly prepares low-added-value products such as fluosilicate, cryolite, wet aluminum fluoride and the like and has the problems of bad working conditions, low resource utilization rate, large three wastes, serious pollution and the like.
In recent years, technical research on preparing hydrogen fluoride by fluosilicic acid is increased by experts in industry, and the thermal decomposition method using hydrogen fluoride as an intermediate product is the most industrialized process route at present, has the advantages of high resource utilization rate, good product quality, diversification, no three-waste emission and the like, but is influenced by industrialized equipment, control and the like in the process of converting the results, and needs to be studied deeply to solve the industrial amplification technical bottleneck.
Disclosure of Invention
The first object of the invention is to provide a preparation method of anhydrous hydrogen fluoride, which can improve the reaction conversion rate, reduce the emission of three wastes and realize clean production.
The second object of the present invention is to provide an apparatus for producing anhydrous hydrogen fluoride, which is dedicated to carrying out the above-mentioned method for producing anhydrous hydrogen fluoride. The device can effectively improve impurity removal efficiency and reaction conversion rate, reduce process energy consumption, and is easy for industrialized implementation and popularization.
In order to achieve the above object, the preparation method of anhydrous hydrogen fluoride of the present invention comprises the steps of:
(1) Carrying out ammonolysis reaction on the ammonium fluosilicate solution and ammonia water, and carrying out solid-liquid separation to obtain an ammonium fluoride solution and white carbon black ointment;
(2) Evaporating, concentrating and thermally decomposing the ammonium fluoride solution to obtain ammonium bifluoride molten liquid;
(3) Reacting the ammonium bifluoride molten liquid with sodium fluoride solution at a temperature of more than 50 ℃, cooling for crystallization, and carrying out solid-liquid separation to obtain sodium bifluoride ointment;
(4) Drying and thermally decomposing the sodium bifluoride ointment to obtain coarse hydrogen fluoride gas and sodium bifluoride, and purifying the coarse hydrogen fluoride gas to obtain anhydrous hydrogen fluoride.
The method can realize the efficient preparation of anhydrous hydrogen fluoride, improve the reaction conversion rate, realize the recycling of substances, reduce the discharge of three wastes and realize clean production.
Further, in the step (3), solid-liquid separation is carried out to obtain the sodium hydrogen fluoride ointment and the ammonium fluoride mother liquor; reaction of potassium fluoride and ammonium fluoride mother liquor to remove SiF 6 2- Obtaining purified mother liquor and potassium fluosilicate precipitate; the purified mother liquor returns to the step (2) for treatment; alternatively, a part of the purification mother liquor and sodium fluoride solution used in the sodium fluoride preparation step (3) in the step (4) are returned to the step (2) for treatment. Further, the molar ratio of potassium fluoride to fluorosilicate is (2-2.1): 1, the reaction temperature is 10-30 ℃ and the reaction time is 10-30 min.
In the ammonolysis reaction process of ammonium fluosilicate and ammonia water, the ammonolysis reaction often cannot be thoroughly carried out, siF inevitably remains in the solution 6 2- . The common method is to introduce ammonia gas into the system to make the reaction proceed forward, but the reaction can reach a dynamic equilibrium state to a certain extent, the effect of continuously introducing ammonia gas is very limited, the production cost is greatly increased, and the method is not suitable for large-scale production application. The invention adds potassium fluoride into ammonium fluoride mother liquor obtained after fusion concentration, thermal decomposition and crystallization filtration to generate potassium fluosilicate precipitate, which can thoroughly remove SiF 6 2- 。
The purification mother liquor is used for preparing sodium fluoride solution and preparing ammonium bifluoride molten liquid, the cost of raw materials of the process is reduced, the waste discharge in the production process is reduced, and clean production is realized.
Further, the molar ratio of ammonium bifluoride to sodium fluoride in the ammonium bifluoride molten liquid in the step (3) is (1 to 1.05): 1, the reaction time is 0.5-1 h, and the reaction temperature is 50-100 ℃; further, the mass fraction of the sodium fluoride solution is 10-30%. The molar ratio, the reaction time and the reaction temperature of the ammonium bifluoride and the sodium fluoride are controlled within proper ranges, so that the reaction can be rapidly carried out, and the production efficiency is improved.
Further, in the step (3), the temperature-reducing crystallization is crystallization which is carried out by reducing the temperature to 10-30 ℃; further, the cooling is performed at a speed of 1 ℃/min, and the crystallization is cooling stirring dynamic crystallization. The sodium bifluoride can be crystallized for a sufficient time in the cooling process by controlling the cooling rate and the crystallization temperature, so that the crystallization is more perfect, the crystallization precipitation of sodium bifluoride from the solution is facilitated, and the reaction yield is improved.
Further, in the step (2), the ammonium fluoride content in the ammonium fluoride solution is concentrated to more than 300g/L by evaporation. The content of ammonium fluoride reaches more than 300g/L after evaporation and concentration, which is favorable for thermal decomposition and improves the yield.
Further, the evaporating concentration temperature in the step (2) is 90-130 ℃. Further, the evaporative concentration is one-effect evaporative concentration, double-effect evaporative concentration or multi-effect evaporative concentration, and the temperature of the evaporative concentration is sequentially increased. Further, the evaporation concentration is double-effect evaporation concentration, wherein the double-effect evaporation concentration comprises first-effect evaporation concentration and second-effect evaporation concentration; the first-effect evaporation concentration temperature is 90-110 ℃, and the second-effect evaporation concentration temperature is 110-130 ℃. According to different temperatures of all evaporation and concentration working sections, cascade utilization of heat energy of the system is realized, and process energy consumption is reduced.
Further, the percentage content of ammonium bifluoride in the ammonium fluoride molten liquid formed after the thermal decomposition in the step (2) is not less than 90%. Controlling the percentage of ammonium bifluoride to be not less than 90% improves the yield of production and improves the purity of the product hydrogen fluoride.
Further, the thermal decomposition temperature in the step (2) is 140-180 ℃. Further, the thermal decomposition is one-stage thermal decomposition, two-stage thermal decomposition or multi-stage thermal decomposition, and the temperatures of the thermal decomposition are set up to be sequentially higher. Further, the thermal decomposition is a two-stage thermal decomposition including a first-stage thermal decomposition and a second-stage thermal decomposition; the first stage thermal decomposition temperature is 140-160 ℃, and the second stage thermal decomposition temperature is 160-180 ℃. According to different temperatures of the thermal decomposition working sections, the cascade utilization of the heat energy of the system is realized, and the process energy consumption is reduced.
Further, the byproduct ammonia generated in the step (1) and the step (2) is absorbed by fluosilicic acid solution; further, the final pH of the fluorosilicic acid absorption liquid is controlled to be 1-2. The ammonium fluosilicate is prepared by adopting the byproduct ammonia gas of the fluosilicic acid solution absorption process, so that the process raw material cost is reduced, and no three wastes are discharged in the process of preparing anhydrous hydrogen fluoride, thereby realizing clean production.
Further, in the step (4), the drying temperature is 60-100 ℃ and the drying time is 1-2 h; the thermal decomposition temperature is 200-450 ℃, and the thermal decomposition time is 0.5-1 h. Drying and thermal decomposition of sodium hydrogen fluoride are carried out step by step, so that the sodium hydrogen fluoride can be dried at a lower temperature without decomposition, the yield is improved, and the water is removed as much as possible; after sufficient drying, thermal decomposition is performed at a higher temperature, which shortens the reaction time and improves the efficiency.
Further, the crude hydrogen fluoride in the step (4) contains PO 4 3- 、SO 4 2- 、SiF 6 2- And impurities such as water; the purification is a common purification means such as washing, rectification, etc. Impurities in the crude hydrogen fluoride gas can be removed through purification treatment, and anhydrous hydrogen fluoride with higher purity is obtained.
Further, the molar ratio of ammonium fluorosilicate to ammonia in the ammonolysis reaction in the step (1) is 1: (4.5-5.5), the reaction temperature is 45-55 ℃, and the reaction time is 10-30 min. The molar ratio of ammonium fluosilicate to ammonia is properly adjusted to enable the ammonium fluosilicate to react more fully, the production yield is improved, the reaction is rapidly carried out by adjusting the temperature, the time cost is saved, and the production efficiency is improved.
Further, the step (1)The medium fluosilicic acid ammonium solution is prepared by reacting fluosilicic acid solution which is a byproduct in the phosphate fertilizer industry with ammonia water and removing phosphorus and sulfur; the dephosphorization and the sulfur removal are to add an iron compound and a lead compound into ammonium fluosilicate solution to react and precipitate PO by stirring 4 3- 、SO 4 2- Ions; the iron compound is at least one of ferric oxide and ferric fluosilicate, and the lead compound is at least one of lead oxide and lead fluosilicate; further, the iron compound is added in the amount of iron element in the iron compound and PO in the ammonium fluosilicate solution 4 3- The molar ratio is 1:1; the addition amount of the lead compound is SO in the lead element in the lead compound and the ammonium fluosilicate solution 4 2- The molar ratio is 1:1. Further, the concentration of the fluosilicic acid solution is 10-35%, the concentration of the ammonia water is 12-17%, and the molar ratio of the fluosilicic acid to the ammonia is 1: (1.6 to the upper limit) 2); the reaction temperature is 35-45 ℃, the time is 10-30 min.
The byproduct fluosilicic acid in the phosphate fertilizer industry is rich in resources and low in cost, and the byproduct in the phosphate fertilizer industry is used as a fluorine source for preparing anhydrous hydrogen fluoride, so that the byproduct in the phosphate fertilizer industry is effectively utilized, the exploitation of fluorite resources is reduced, the production cost of the anhydrous hydrogen fluoride is reduced, and the economic benefit is very high.
PO is unavoidable in fluosilicic acid solution as byproduct in phosphate fertilizer industry 4 3- And SO 4 2- Because the acidity of the fluosilicic acid solution is large, the direct dephosphorization and the sulfur removal can dissolve the precipitate generated by the reaction in the fluosilicic acid solution, which is unfavorable for PO 4 3- And SO 4 2- Is removed. The invention introduces ammonia gas into fluosilicic acid solution to convert fluosilicic acid into ammonium fluosilicate and change pH of the solution, and then carries out reaction to remove PO 4 3- And SO 4 2- And the dissolution of the precipitate can be reduced, the impurity removal efficiency is improved, the accumulation of impurity ions is reduced, the occurrence of side reactions in a system is avoided, and the product purity and the reaction efficiency are improved.
The invention relates to a preparation device of anhydrous hydrogen fluoride, which is specially used for implementing the preparation method of the anhydrous hydrogen fluoride, and comprises an ammonolysis device for ammonolysis of an ammonium fluosilicate solution, a first solid-liquid separation device connected to the downstream of the ammonolysis device, wherein the first solid-liquid separation device is provided with a liquid outlet, the liquid outlet is sequentially connected with an evaporation concentration device and a thermal decomposition device, the thermal decomposition device is provided with an ammonium bifluoride molten liquid outlet, the ammonium bifluoride molten liquid outlet is connected with a sodium bifluoride production device, the sodium bifluoride production device is provided with a sodium fluoride solution inlet, the ammonium bifluoride molten liquid and the sodium fluoride solution react in the sodium bifluoride production device to generate sodium bifluoride, the sodium bifluoride production device is provided with a reaction liquid outlet, the reaction liquid outlet is connected with a sodium bifluoride crystallization device, the downstream of the sodium bifluoride crystallization device is connected with a second solid outlet of the second solid-liquid separation device, and the solid outlet of the second solid-liquid separation device is sequentially connected with a sodium bifluoride ointment drying device, a sodium bifluoride ointment thermal decomposition device and a crude hydrogen fluoride gas purification device, so as to sequentially obtain the final purified hydrogen fluoride.
Further, the second solid-liquid separation device is provided with a liquid outlet, and the liquid outlet is connected with a device for removing SiF 6 2- The downstream of the mother liquor treatment tank is connected with the evaporation concentration device for conveying purified mother liquor produced by the mother liquor treatment tank into the evaporation concentration device.
Further, the downstream of the mother liquor treatment tank is also connected with a sodium fluoride solution preparation tank, and the sodium fluoride solution preparation tank is connected with a sodium fluoride solution inlet on the sodium hydrogen fluoride production device.
Further, the sodium bifluoride ointment thermal decomposition device is provided with a sodium fluoride outlet, and the sodium fluoride outlet is connected with the sodium fluoride solution configuration tank.
Further, the preparation device of anhydrous hydrogen fluoride further comprises an ammonium fluosilicate solution production device and a impurity removing device, wherein the ammonium fluosilicate solution production device is used for preparing the ammonium fluosilicate solution through reaction of the ammonium fluosilicate solution and ammonia, the impurity removing device is provided with a liquid inlet and a liquid outlet, the liquid outlet of the impurity removing device is connected with the ammonolysis device, and the liquid inlet of the impurity removing device is connected with the ammonium fluosilicate solution production device and is used for removing impurities from the ammonium fluosilicate solution.
Further, the ammonia outlets of the ammonium fluosilicate production device, the ammonolysis device, the evaporation concentration device and the thermal decomposition device are respectively connected with the air inlet of the tail gas absorption device.
Drawings
FIG. 1 is a schematic diagram of the process flow of a method and apparatus for preparing anhydrous hydrogen fluoride according to the present invention. In fig. 1, the components represented by the respective reference numerals are as follows:
1. a first continuous flow reactor; 2. a impurity removal tank; 3. a second continuous flow reactor; 4. a first filtering device; 5. an evaporation system; 6. a thermal decomposition system; 7. a third continuous flow reactor; 8. a crystallization tank; 9. a second filtering device; 10. a primary converter; 11. a secondary converter; 12. a rectification system; 13. a sodium fluoride solution preparing tank; 14. mother liquor treatment tank.
Detailed Description
The technical scheme of the invention is further described below with reference to the specific embodiments.
1. Examples of the apparatus for producing anhydrous hydrogen fluoride according to the present invention
The specific embodiment of the anhydrous hydrogen fluoride preparation device comprises an ammonium fluosilicate production device, a impurity removal device, an ammonolysis device, a first solid-liquid separation device, an evaporation concentration device, a thermal decomposition device, a sodium hydrogen fluoride production device, a sodium hydrogen fluoride crystallization device, a second solid-liquid separation device, a sodium hydrogen fluoride ointment drying device, a sodium hydrogen fluoride ointment thermal decomposition device, a crude hydrogen fluoride gas purification device, a sodium fluoride configuration tank, a mother liquor treatment tank and a tail gas absorption device, as shown in figure 1.
The production device of the ammonium fluosilicate is a first continuous flow reactor 1, and is used for reacting fluosilicic acid solution with ammonia water to obtain ammonium fluosilicate, wherein the first continuous flow reactor 1 is connected with a fluosilicic acid raw material pipe and an ammonia water raw material pipe, and the downstream is connected with a impurity removing device. The impurity removing device is an impurity removing groove 2 and is used for removing impurities of ammonium fluosilicate, and a liquid outlet of the impurity removing device is connected with the ammonolysis device. The ammonolysis device is a second continuous flow reactor 3 which is used for ammonolysis reaction of the ammonium fluosilicate solution, and the downstream is connected with a first solid-liquid separation device. The first solid-liquid separation device is a first filtering device 4 and is used for separating ammonium fluoride solution and white carbon black ointment, and a liquid outlet of the first filtering device 4 is connected with the evaporation concentration device. The evaporation concentration device is an evaporation system 5 and is used for evaporating and concentrating the ammonium fluoride solution, and the downstream is connected with the thermal decomposition device. The thermal decomposition device is a thermal decomposition system 6 for thermally decomposing ammonium fluoride to obtain ammonium bifluoride, and the downstream is connected with a sodium bifluoride production device. The sodium bifluoride production device is a third continuous flow reactor 7 and is used for preparing sodium bifluoride by reacting ammonium bifluoride with sodium fluoride, and the downstream is connected with a sodium bifluoride crystallization device. The sodium hydrogen fluoride crystallization device is a crystallization tank 8 and is used for cooling and crystallizing sodium hydrogen fluoride slurry, and the downstream is connected with a second solid-liquid separation device. The second solid-liquid separation device is a second filtering device 9 and is used for separating sodium hydrogen fluoride ointment, and the downstream is sequentially connected with a sodium hydrogen fluoride ointment drying device, a sodium hydrogen fluoride ointment thermal decomposition device and a crude hydrogen fluoride gas purification device. The sodium hydrogen fluoride ointment drying device is a primary converter 10 and is used for drying sodium hydrogen fluoride ointment; the sodium hydrogen fluoride ointment thermal decomposition device is a secondary converter 11 and is used for thermal decomposition of sodium hydrogen fluoride; the crude hydrogen fluoride gas purifying device is a rectifying system 12 for rectifying and purifying the crude hydrogen fluoride gas. The second filtering device 9 is also provided with a liquid outlet, the liquid outlet is connected with a mother liquor treatment tank 14, the downstream of the mother liquor treatment tank 14 is connected with an evaporation concentration device and a sodium fluoride solution preparation tank 13, and the sodium fluoride solution preparation tank 13 is connected with a sodium fluoride solution inlet on the sodium hydrogen fluoride production device. The sodium bifluoride paste pyrolysis apparatus has a sodium fluoride outlet connected to a sodium fluoride solution preparing tank 13. The ammonia outlets of the first continuous flow reactor 1, the second continuous flow reactor 3, the evaporation system 5 and the thermal decomposition system 6 are respectively connected with the air inlets of the tail gas absorbing device, and the tail gas treating device is a three-stage absorbing tower and is used for absorbing and treating ammonia generated in the reaction process.
2. Examples of the method for producing anhydrous hydrogen fluoride according to the present invention
Example 1
The preparation method of the anhydrous hydrogen fluoride comprises the following steps:
(1) According to fluorineThe molar ratio of silicic acid to ammonia is 1:1.6, 10% fluosilicic acid solution and 17% ammonia water which are byproducts of the phosphate fertilizer industry are simultaneously introduced into a first continuous flow reactor, the reaction temperature is controlled to be 40 ℃, the reaction time is controlled to be 20min, and the ammonium fluosilicate solution is obtained by reaction. Then according to the iron element in the iron compound and PO in the ammonium fluosilicate solution 4 3- The molar ratio is 1:1, and the lead element in the lead compound and SO in the ammonium fluosilicate solution 4 2- Adding an iron compound and a lead compound in a molar ratio of 1:1, stirring for reaction, and filtering to obtain a treated ammonium fluosilicate solution. The iron compound is ferric oxide, and the lead compound is lead oxide.
In other embodiments the iron compound may be any one of iron oxide and iron fluosilicate; the lead compound may be any one of lead oxide and lead fluorosilicate.
(2) And simultaneously introducing the treated ammonium fluosilicate solution and 17% ammonia water into a second continuous flow reactor according to the mol ratio of the ammonium fluosilicate to the ammonia of 1:5.5, controlling the reaction temperature to be 50 ℃ and the reaction time to be 20min, filtering and separating after the reaction to obtain an ammonium fluoride solution and white carbon black ointment, washing and drying the ointment to obtain a white carbon black product.
(3) And (3) sending the ammonium fluoride solution obtained in the step (2) into a double-effect evaporation system, controlling the first-effect evaporation temperature to 90 ℃, controlling the second-effect evaporation temperature to 120 ℃, gradually concentrating (the ammonium fluoride content is 300 g/L), then sending the ammonium fluoride solution into a two-stage thermal decomposition system, controlling the temperature of the first-stage thermal decomposition system to 140 ℃, controlling the temperature of the second-stage thermal decomposition system to 160 ℃, obtaining ammonium bifluoride molten liquid, and detecting the purity of ammonium bifluoride to 90.5%.
(4) Adding sodium fluoride into water to prepare 30% sodium fluoride solution, then introducing the solution and ammonium bifluoride molten liquid obtained in the step (3) into a third continuous flow reactor, controlling the molar ratio of sodium fluoride to ammonium bifluoride to be 1:1, controlling the reaction temperature to be 100 ℃, controlling the reaction time to be 0.5h, flowing into a crystallization tank after the reaction to stir and crystallize, controlling the cooling rate to be 1 ℃/min, cooling to 30 ℃, and filtering and washing to obtain sodium bifluoride ointment and ammonium bifluoride mother liquor.
(5) Introducing the ammonium fluoride mother liquor obtained in the step (4) into a mother liquor treatment tank, wherein the molar ratio of potassium fluoride to fluorosilicate in the ammonium fluoride mother liquor is 2:1, adding potassium fluoride in proportion for reaction, controlling the reaction temperature to be 30 ℃ and the reaction time to be 10min, filtering to obtain purified mother liquor and potassium fluosilicate precipitate, and taking out after potassium fluosilicate precipitate treatment.
(6) Sequentially feeding the sodium hydrogen fluoride ointment obtained in the step (4) into a primary converter, and controlling the drying temperature to be 60 ℃ and the drying time to be 2 hours; and (3) feeding the dried sodium bifluoride solid into a secondary converter for thermal decomposition, controlling the thermal decomposition temperature to be 450 ℃ and the thermal decomposition time to be 0.5h, and rectifying and purifying the obtained crude hydrogen fluoride gas to obtain anhydrous hydrogen fluoride, wherein the sodium fluoride is recycled for preparing sodium fluoride solution.
(7) And (3) enabling the ammonia gas as a process byproduct to enter a three-stage absorption tower, absorbing with an industry byproduct fluosilicic acid solution, controlling the end point of the absorption liquid to control the pH value to be 2, obtaining an ammonium fluosilicic acid solution, and returning the ammonium fluosilicic acid solution to a second continuous flow reactor for ammonolysis reaction.
Example 2
The preparation method of the anhydrous hydrogen fluoride comprises the following steps:
(1) And simultaneously introducing 20% fluosilicic acid solution and 15% ammonia water which are byproducts of the phosphate fertilizer industry into a first continuous flow reactor according to the molar ratio of fluosilicic acid to ammonia of 1:1.8, controlling the reaction temperature to be 35 ℃ and the reaction time to be 30min, and reacting to obtain ammonium fluosilicate solution. Then according to the iron element in the iron compound and PO in the ammonium fluosilicate solution 4 3- The molar ratio is 1:1, and the lead element in the lead compound and SO in the ammonium fluosilicate solution 4 2- Adding an iron compound and a lead compound in a molar ratio of 1:1, stirring for reaction, and filtering to obtain a treated ammonium fluosilicate solution.
(2) And simultaneously introducing the treated ammonium fluosilicate solution and 15% ammonia water into a second continuous flow reactor according to the mol ratio of the ammonium fluosilicate to the ammonia of 1:5, controlling the reaction temperature to be 45 ℃ and the reaction time to be 30min, filtering and separating after the reaction to obtain an ammonium fluoride solution and white carbon black ointment, washing the ointment, and drying to obtain a white carbon black product.
(3) And (3) sending the ammonium fluoride solution obtained in the step (2) into a double-effect evaporation system, controlling the first-effect evaporation temperature to 90 ℃, controlling the second-effect evaporation temperature to 110 ℃, gradually concentrating (the ammonium fluoride content is 360 g/L), then sending the ammonium fluoride solution into a two-stage thermal decomposition system, controlling the temperature of the first-stage thermal decomposition system to 150 ℃, controlling the temperature of the second-stage thermal decomposition system to 170 ℃, obtaining ammonium bifluoride molten liquid, and detecting the purity of ammonium bifluoride to be 93.2%.
(4) Adding sodium fluoride into a purification mother solution (the purification mother solution obtained by filtering in the step (5)) to prepare a 20% sodium fluoride solution, then introducing the solution and the ammonium bifluoride molten liquid obtained in the step (3) into a third continuous flow reactor simultaneously, controlling the molar ratio of the sodium fluoride to the ammonium bifluoride to be 1:1.05, controlling the reaction temperature to be 70 ℃ and the reaction time to be 40min, flowing into a crystallization tank after the reaction to stir and crystallize, controlling the cooling rate to be 1 ℃/min, cooling to 20 ℃, and filtering and washing to obtain sodium bifluoride ointment and ammonium bifluoride mother solution.
(5) Introducing the ammonium fluoride mother liquor obtained in the step (4) into a mother liquor treatment tank, wherein the molar ratio of potassium fluoride to fluorosilicate in the ammonium fluoride mother liquor is 2.02:1, adding potassium fluoride in proportion for reaction, controlling the reaction temperature to be 20 ℃ and the reaction time to be 20min, filtering to obtain purified mother liquor and potassium fluosilicate precipitate, and processing the potassium fluosilicate precipitate and taking out.
(6) The sodium hydrogen fluoride ointment obtained in the step (4) sequentially enters a primary converter, controlling the drying temperature to be 80 ℃ and the drying time to be 1.5 hours; and (3) putting the dried sodium hydrogen fluoride solid into a secondary converter for thermal decomposition, controlling the thermal decomposition temperature to be 350 ℃ and the thermal decomposition time to be 40min, and rectifying and purifying the obtained crude hydrogen fluoride gas to obtain anhydrous hydrogen fluoride.
(7) The ammonia gas as a byproduct of the process enters a three-stage absorption tower, the ammonia gas is absorbed by an industry byproduct fluosilicic acid solution, the end point of the absorption solution is controlled to be 1, the ammonium fluosilicic acid solution is obtained, and the ammonium fluosilicic acid solution is returned to a second continuous flow reactor for ammonolysis reaction.
Example 3
The preparation method of the anhydrous hydrogen fluoride comprises the following steps:
(1) And simultaneously introducing 35% fluosilicic acid solution and 12% ammonia water which are byproducts of the phosphate fertilizer industry into a first continuous flow reactor according to the mol ratio of fluosilicic acid to ammonia of 1:2, controlling the reaction temperature to be 45 ℃ and the reaction time to be 10min, and reacting to obtain ammonium fluosilicate solution. According to PO in ammonium fluorosilicate solution 4 3- With iron compounds middle iron elementThe molar ratio of the elements is 1:1, SO in the ammonium fluosilicate solution 4 2- Adding an iron compound and a lead compound in a molar ratio of 1:1 with the lead compound, stirring for reaction, and filtering to obtain a treated ammonium fluosilicate solution.
(2) And simultaneously introducing the treated ammonium fluosilicate solution and 12% ammonia water into a second continuous flow reactor according to the mol ratio of the ammonium fluosilicate to the ammonia of 1:4.5, controlling the reaction temperature to 55 ℃ and the reaction time to 10min, filtering and separating after the reaction to obtain an ammonium fluoride solution and white carbon black ointment, washing the ointment, and drying to obtain a white carbon black product.
(3) Mixing the ammonium fluoride solution obtained in the step (2) with the recycled purification mother solution, feeding the mixture into a double-effect evaporation system, controlling the first-effect evaporation temperature to be 110 ℃, controlling the second-effect evaporation temperature to be 130 ℃, concentrating step by step (the ammonium fluoride content is 410 g/L), feeding the mixture into a two-stage thermal decomposition system, controlling the temperature of the first-stage thermal decomposition system to be 160 ℃, controlling the temperature of the second-stage thermal decomposition system to be 180 ℃, obtaining ammonium bifluoride molten liquid, and detecting the purity of ammonium bifluoride to be 94.3%.
(4) Adding sodium fluoride into the purification mother liquor (the purification mother liquor obtained by filtering in the step (5)) to prepare a 10% sodium fluoride solution, and then introducing the 10% sodium fluoride solution and the ammonium bifluoride molten liquid obtained in the step (3) into a third continuous flow reactor simultaneously to control sodium fluoride: the molar ratio of the ammonium bifluoride is 1:1.02, the reaction temperature is 50 ℃, the reaction time is 1h, the mixture flows into a crystallization tank for stirring and crystallization after the reaction, the cooling rate is controlled to be 1 ℃/min, and the sodium bifluoride ointment and ammonium fluoride mother liquor are obtained after the cooling to 10 ℃ and the filtration and the washing.
(5) Introducing the ammonium fluoride mother liquor obtained in the step (4) into a mother liquor treatment tank, wherein the molar ratio of potassium fluoride to fluorosilicate in the ammonium fluoride mother liquor is 2:1, adding potassium fluoride in proportion for reaction, controlling the reaction temperature to be 10 ℃ and the reaction time to be 30min, filtering to obtain purified mother liquor and potassium fluosilicate precipitate, and taking out after potassium fluosilicate precipitate treatment.
(6) Sequentially feeding the sodium hydrogen fluoride ointment obtained in the step (4) into a primary converter, and controlling the drying temperature to be 100 ℃ and the drying time to be 1h; and (3) putting the dried sodium hydrogen fluoride solid into a secondary converter for thermal decomposition, controlling the thermal decomposition temperature to be 200 ℃ and the thermal decomposition time to be 1h, and rectifying and purifying the obtained crude hydrogen fluoride gas to obtain anhydrous hydrogen fluoride.
(7) And (3) enabling the ammonia gas as a process byproduct to enter a three-stage absorption tower, absorbing the ammonia gas with the treated fluosilicic acid solution, controlling the end point of the absorption liquid to control the pH value to be 1.5, obtaining ammonium fluosilicic acid solution, and returning the ammonium fluosilicic acid solution to the second continuous flow reactor for ammonolysis reaction.
3. Experimental example
The electronic grade hydrogen fluoride and white carbon black products in the examples were tested in this experimental example, and the results are shown in tables 1-2.
TABLE 1 quality test results of anhydrous hydrogen fluoride products obtained in examples 1-3
TABLE 2 whites obtained in examples 1-3 product quality detection results of carbon black
As shown in the data in the table, the anhydrous hydrogen fluoride product obtained by the invention has high purity, low impurity content and better index than the national standard requirement; the white carbon black product meets the requirements of corresponding industry standards.
Claims (9)
1. A method for preparing anhydrous hydrogen fluoride, comprising the steps of:
(1) Carrying out ammonolysis reaction on the ammonium fluosilicate solution and ammonia water, and carrying out solid-liquid separation to obtain an ammonium fluoride solution and white carbon black ointment;
(2) Evaporating, concentrating and thermally decomposing the ammonium fluoride solution to obtain ammonium bifluoride molten liquid;
(3) Reacting the ammonium bifluoride molten liquid with sodium fluoride solution at a temperature of more than 50 ℃, cooling for crystallization, and carrying out solid-liquid separation to obtain sodium bifluoride ointment;
(4) Drying and thermally decomposing the sodium bifluoride ointment to obtain crude hydrogen fluoride gas and sodium fluoride, and purifying the crude hydrogen fluoride gas to obtain anhydrous hydrogen fluoride;
the ammonium fluosilicate solution in the step (1) is prepared by reacting fluosilicic acid solution which is a byproduct in the phosphate fertilizer industry with ammonia water and removing phosphorus and sulfur; the dephosphorization and the sulfur removal are to add an iron compound and a lead compound into ammonium fluosilicate solution to react and precipitate PO by stirring 4 3- 、SO 4 2- Ions; the molar ratio of fluosilicic acid to ammonia is 1: (1.6-2); the iron compound is at least one of ferric oxide and ferric fluosilicate, and the lead compound is at least one of lead oxide and lead fluosilicate;
the dephosphorization and the desulfurization are that ammonia gas is firstly introduced into ammonium fluosilicate solution, and then PO is removed by reaction 4 3- 、SO 4 2- Ions;
the cooling crystallization in the step (3) is to cool to 10-30 ℃, the cooling is carried out at a speed of 1 ℃/min, and the crystallization is cooling stirring dynamic crystallization.
2. The method for producing anhydrous hydrogen fluoride according to claim 1, wherein the sodium hydrogen fluoride ointment and ammonium fluoride mother liquor are obtained by solid-liquid separation in the step (3); reaction of potassium fluoride and ammonium fluoride mother liquor to remove SiF 6 2- Carrying out ion to obtain purified mother liquor and potassium fluosilicate precipitate; the purified mother liquor returns to the step (2) for treatment;
alternatively, a part of the purification mother liquor and sodium fluoride solution used in the sodium fluoride preparation step (3) in the step (4) are returned to the step (2) for treatment.
3. The process for producing anhydrous hydrogen fluoride according to claim 1, wherein the molar ratio of ammonium bifluoride to sodium fluoride in the ammonium bifluoride melt liquid in step (3) is (1 to 1.05): 1, the reaction time is 0.5-1 h, and the reaction temperature is 50-100 ℃.
4. The process for producing anhydrous hydrogen fluoride according to claim 1, wherein the concentration by evaporation in the step (2) is performed by concentrating the ammonium fluoride content in the ammonium fluoride solution to 300g/L or more by evaporation.
5. The process for producing anhydrous hydrogen fluoride according to claim 1 or 4, wherein the evaporation concentration temperature in step (2) is 90 to 130 ℃.
6. The process for producing anhydrous hydrogen fluoride according to claim 1, wherein the percentage of ammonium bifluoride in the ammonium bifluoride molten liquid formed after the thermal decomposition in step (2) is not less than 90%.
7. The method for producing anhydrous hydrogen fluoride according to claim 1 or 6, wherein the thermal decomposition temperature in step (2) is 140 to 180 ℃.
8. The process for producing anhydrous hydrogen fluoride according to claim 1, wherein the drying temperature in step (4) is 60 to 100 ℃ and the drying time is 1 to 2 hours; the thermal decomposition temperature is 200-450 ℃, and the thermal decomposition time is 0.5-1 h.
9. The preparation method of anhydrous hydrogen fluoride is characterized by comprising an ammonolysis device for ammonolysis of ammonium fluosilicate solution, a first solid-liquid separation device connected to the downstream of the ammonolysis device, wherein the first solid-liquid separation device is provided with a liquid outlet, the liquid outlet is sequentially connected with an evaporation concentration device and a thermal decomposition device, the thermal decomposition device is provided with an ammonium bifluoride molten liquid outlet, the ammonium bifluoride molten liquid outlet is connected with a sodium bifluoride production device, the sodium bifluoride production device is provided with a sodium fluoride solution inlet, the ammonium bifluoride molten liquid and the sodium fluoride solution react in the sodium bifluoride production device to generate sodium bifluoride, the sodium bifluoride production device is provided with a reaction liquid outlet, the reaction liquid outlet is connected with a sodium bifluoride crystallization device, the downstream of the sodium bifluoride crystallization device is connected with a second solid-liquid separation device, the solid outlet of the second solid-liquid separation device is sequentially connected with a sodium bifluoride drying device, a sodium bifluoride ointment thermal decomposition device and a crude hydrogen fluoride gas purification device, so as to sequentially produce dry and crude hydrogen fluoride gas, and finally obtain crude hydrogen fluoride, and finally obtain anhydrous hydrogen fluoride;
the preparation device of anhydrous hydrogen fluoride further comprises an ammonium fluosilicate solution production device and a impurity removing device, the ammonium fluosilicate solution production device is used for preparing the ammonium fluosilicate solution through reaction of the ammonium fluosilicate solution and ammonia, the impurity removing device is provided with a liquid inlet and a liquid outlet, the liquid outlet of the impurity removing device is connected with the ammonolysis device, and the liquid inlet of the impurity removing device is connected with the ammonium fluosilicate solution production device and is used for removing impurities from the ammonium fluosilicate solution.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144315A (en) * | 1976-08-26 | 1979-03-13 | Goulding Chemicals Limited | Production of hydrogen fluoride |
| CN102795601A (en) * | 2011-05-27 | 2012-11-28 | 多氟多化工股份有限公司 | Method for producing anhydrous hydrogen fluoride and coproducing silica white from low-grade fluorine resources |
| CN103342365A (en) * | 2013-06-24 | 2013-10-09 | 嵩县开拓者钼业有限公司 | Silicon-containing mineral processing method |
| CN107055477A (en) * | 2017-04-26 | 2017-08-18 | 衢州市鼎盛化工科技有限公司 | The method and its device of hydrogen fluoride are prepared by fluosilicic acid |
| CN111729494A (en) * | 2020-06-08 | 2020-10-02 | 江西渠成氟化学有限公司 | Hydrogen fluoride tail gas treatment method |
| CN113860258A (en) * | 2021-11-04 | 2021-12-31 | 多氟多新材料股份有限公司 | Preparation method of hydrogen fluoride |
-
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- 2022-04-28 CN CN202210471104.5A patent/CN114804030B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144315A (en) * | 1976-08-26 | 1979-03-13 | Goulding Chemicals Limited | Production of hydrogen fluoride |
| CN102795601A (en) * | 2011-05-27 | 2012-11-28 | 多氟多化工股份有限公司 | Method for producing anhydrous hydrogen fluoride and coproducing silica white from low-grade fluorine resources |
| CN103342365A (en) * | 2013-06-24 | 2013-10-09 | 嵩县开拓者钼业有限公司 | Silicon-containing mineral processing method |
| CN107055477A (en) * | 2017-04-26 | 2017-08-18 | 衢州市鼎盛化工科技有限公司 | The method and its device of hydrogen fluoride are prepared by fluosilicic acid |
| CN111729494A (en) * | 2020-06-08 | 2020-10-02 | 江西渠成氟化学有限公司 | Hydrogen fluoride tail gas treatment method |
| CN113860258A (en) * | 2021-11-04 | 2021-12-31 | 多氟多新材料股份有限公司 | Preparation method of hydrogen fluoride |
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